US20230407195A1 - Process for treating a feedstock comprising halides - Google Patents
Process for treating a feedstock comprising halides Download PDFInfo
- Publication number
- US20230407195A1 US20230407195A1 US18/252,100 US202118252100A US2023407195A1 US 20230407195 A1 US20230407195 A1 US 20230407195A1 US 202118252100 A US202118252100 A US 202118252100A US 2023407195 A1 US2023407195 A1 US 2023407195A1
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- stream
- outlet
- inlet
- separation
- hydrotreatment
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 150000004820 halides Chemical class 0.000 title claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 64
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 64
- 229910001868 water Inorganic materials 0.000 claims abstract description 62
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 56
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- -1 ammonium halides Chemical class 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 23
- 238000001556 precipitation Methods 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 238000004891 communication Methods 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 14
- 239000008213 purified water Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000012267 brine Substances 0.000 claims description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 7
- 239000002699 waste material Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000012620 biological material Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000004230 steam cracking Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 2
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000047 product Substances 0.000 description 47
- 239000012071 phase Substances 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 17
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- 229910001502 inorganic halide Inorganic materials 0.000 description 11
- 125000005842 heteroatom Chemical group 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- 239000011149 active material Substances 0.000 description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011143 downstream manufacturing Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 2
- 239000001284 azanium sulfanide Substances 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005695 dehalogenation reaction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 229910001872 inorganic gas Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010936 aqueous wash Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
- C10G31/08—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by treating with water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
-
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/06—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a selective hydrogenation of the diolefins
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/80—Additives
- C10G2300/805—Water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Definitions
- This invention relates to a process and a system for conversion of a hydrocarbonaceous feed comprising halides and nitrogen, and specifically a process and a system for removing ammonium halides from a hydrocarbon stream comprising ammonia and one or more halides.
- Refinery and petrochemical processes comprise a plurality of treatments of hydrocarbon rich streams in order to provide products or intermediates in the form of LPG, naphtha, gasoline, diesel, etc.
- Such treatments comprise hydro-treatment, hydro-cracking, steam-cracking, fractionation and stripping, as well as intermediate heat exchange and removal of impurities.
- Hydrocarbonaceous feedstock may, depending on origin, contain heteroatoms, undesired in the downstream processing.
- the most abundant heteroatoms are sulfur, nitrogen and, oxygen, which may be present in concentrations from 100 ppm w to 10 wt %, and for oxygen in some biological materials even as high as 45 wt %.
- These heteroatoms are in refinery hydrotreatment processes converted into hydrogen sulfide, ammonia, water and carbon oxides, which cause few challenges in the process plants.
- Other heteroatoms are typically metals, which typically are present in small amounts (0-10 ppm w ) and precipitate on catalyst guard particles, and thus also cause few challenges in the process plants.
- heteroatoms may be present in much higher concentrations than in fossil feedstocks.
- the content of e.g. Cl may be 1000 ppm w or higher, and after hydrotreatment the organic Cl will have been converted to HCl which may cause corrosion issues, especially if the acidity of HCl is not neutralized by presence of e.g. NH 3 . It is therefore important to remove the heteroatoms early in the process, to minimize the effect on down-stream process steps. Similar issues may also be observed for biomass comprising halides, e.g. if originating from salt water.
- WO 2015/050635 relates to a process for hydrotreating and removing halides from a hydrocarbon stream by hydrotreatment.
- the document is silent on the amount of water required for withdrawal of halides from the process and on the practical aspects of the process, except for an emphasis on the materials used being corrosion resistant.
- nitrogen is also present in the hydrocarbons feedstocks.
- organically bound nitrogen is converted to ammonia.
- Ammonia and halides may react to form salts, e.g. ammonium chloride, which is a solid at temperatures below the precipitation temperature which typically is 150° C. to 300° C. Precipitation of such salts may result in partial or complete blocking of process lines as well as potential corrosion and must therefore be avoided. Therefore, it is important to ensure the process temperature to be above the precipitation temperature.
- the hydrocarbon product is washed with water which dissolves inorganic halides and ammonia and may be separated from the hydrocarbon stream.
- the inorganic halides from the hydrocarbon stream are removed from the product.
- These inorganic halides removed from the hydrocarbon stream may be taken away from the system in a dilute aqueous wash water solution, or e.g. by regenerating the wash water by evaporation, membrane separation, reverse osmosis or other means of concentrating the impurities in a brine.
- a make-up hydrogen stream is added to the hydrogen rich gas phase prior to the recycling into the hydrotreatment reactor. This is in order to ensure the required hydrogen to be present within the hydrotreatment reactor for the conversion of organic halides into inorganic halides, and possibly also further reactions, such as olefin saturation.
- a material catalytically active in converting organic halides into inorganic halides is meant to denote catalyst material arranged for and/or suitable for catalyzing the conversion to a commercially relevant extent.
- Organic halides are chemical compounds in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms (fluorine, chlorine, bromine, iodine or astatine—group 17 in current IUPAC terminology).
- “Inorganic halides” are chemical compounds between a halogen atom and an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluoride, chloride, bromide, iodide, or astatide compound, with the further limitation that carbon is not part of the compound.
- a typical example of a material catalytically active would be a classical refinery hydrotreatment catalyst, such as one or more sulfided base metals on a refractive support.
- removing halides is meant to include situations where either some or all of the halides present in organic form are converted into inorganic halides, and subsequently removed. The term is thus, unless otherwise indicated, not limited to situation where a certain percentage of the halides present are removed.
- react at the presence of the catalytically active material is meant to cover bringing a stream into contact with the catalytically active material under effective conditions for the implied catalytic reaction to take place. Such conditions typically relate to temperature, pressure and stream composition.
- precipitation temperature of ammonium halides is meant to cover the temperature (under the given conditions, such as concentration and pressure) at which gaseous ammonia and gaseous inorganic halides (typically hydrogen halides) precipitate, either by reacting to form solid ammonium halide crystals or dissolved in condensed water.
- gaseous ammonia and gaseous inorganic halides typically hydrogen halides
- precipitate temperature either by reacting to form solid ammonium halide crystals or dissolved in condensed water.
- this temperature is 280° C. as an example, and typically for the relevant conditions this temperature will be in the range 150-300° C.
- thermal decomposition shall for convenience be used broadly for any decomposition process, in which a material is partially decomposed at elevated temperature (typically 250° C. to 800° C. or perhaps 1000° C.), in the presence of substoichiometric amount of oxygen (including no oxygen).
- elevated temperature typically 250° C. to 800° C. or perhaps 1000° C.
- oxygen including no oxygen
- the product will typically be a combined liquid and gaseous stream, as well as an amount of solid char.
- the term shall be construed to included processes known as pyrolysis, partial combustion, or hydrothermal liquefaction.
- Barg shall in compliance with the practice of the field be used to denote Bar, gauge, i.e. the pressure relative to atmospheric pressure.
- a broad aspect of the present disclosure relates to a process for conversion of a hydrocarbonaceous feed comprising at least 10 ppm w , 100 ppm w or 500 ppm w and less than 1000 ppm w , 5000 ppm w or 10000 ppm w of one or more halides, and at least 20 ppm w , 100 ppm w or 500 ppm w and less than 1000 ppm w , 5000 ppm w or 10000 ppm w organically bound nitrogen, to a hydrocarbon product stream by hydrotreatment, in the presence of a material catalytically active in hydrotreatment and an amount of hydrogen, wherein said hydrocarbon product stream comprises an amount of ionic halides and an amount of ammonia, said process comprising the steps of
- the first separation temperature being above the precipitation temperature of the ammonium halides present in the mixed product stream.
- said stripping process employs hydrogen, steam, methane or nitrogen as a stripping medium.
- stripping media have the associated benefits of being available in specific processes.
- Hydrogen is also a reagent and may be beneficial since no additional reagents are added to the process and as such it is the preferred stripping medium.
- Steam may be conveniently compatible with the later water addition and methane and nitrogen may also be beneficial due to availability in specific processes.
- the temperature of said first separation step is above 280° C., 300° C. or 320° C. This choice of temperature has the benefit of being conveniently above the precipitation temperature of the ammonium halides, such that these are maintained in gas phase until combination with water.
- the temperature of said first separation step is below the temperature at which 30%, 50% or 80% of the mixed product stream boils. This choice of temperature has the benefit of ensuring that at least 70%, 50% or 20% of the mixed product stream is withdrawn as a liquid from the first separator, to minimize the size of equipment in the overhead stream.
- said polar stream of wash water comprising ammonium halides is directed to a means of concentrating, to provide a stream of purified water and a stream of brine having a concentration of ammonium halides being more than 2 times, 5 times or 10 times and less than 50 times or 100 times above that of the polar stream of wash water comprising ammonium halides.
- a process for conversion of a raw feed stream rich in molecules comprising C, H, N and one or more halides, and optionally O, Si, and other elements, said process comprising
- said raw feed stream is as a mixture rich in plastic, lignin, straw, lignocellulosic biomass, halide contaminated waste oils or aquatic biological material. This has the associated benefit of transforming such inexpensive or greenhouse gas emission favorable raw materials into a valuable purified hydrocarbon.
- said hydrotreatment step is followed by the step of directing the hydrocarbon product and/or the bottoms stream to a steam-cracking process.
- a further aspect relates to a system for hydrotreatment of a hydrocarbonaceous stream comprising
- This system has the associated benefit of being well suited for hydrotreatment with purification of the product hydrocarbon stream and the bottoms stream, minimizing the equipment required to be made of high grade steel.
- said first means of separation is a stripper further having a stripping medium inlet.
- a stripper further having a stripping medium inlet.
- Such a system has the associated benefit of the stripping medium driving dissolved gases, such as ammonia and inorganic halides out of the liquid phase of the hydrocarbon product stream.
- said system for hydrotreatment of a hydrocarbonaceous stream further comprises a means of concentrating, having an inlet, a concentrated brine outlet and a purified water outlet,
- the process and the system disclosed may be found useful where the feed to a hydrotreatment process comprises halides.
- feeds include the products of processes such as hydrotreatment of the product from thermal decomposition of halide rich materials, such as waste plastic, comprising e.g. PVC or other halide containing plastics as well as of biological materials with high halide content, e.g. straw and algae, as well as other products of thermal decomposition or hydrothermal liquefication processes, kerogenic feeds such as coal tar or shale oil.
- the feed comprising halides may also originate from non-pyrolyzed renewable feedstocks, e.g. waste cooking oil, algae lipids, especially when grown in salt water, or other biological feeds comprising hydrocarbons, nitrogen and chloride.
- Ammonia and halides react to form salts, e.g. ammonium chloride, at temperatures below the precipitation temperature typically 150° C. to 300° C. Precipitation of such salts may result in partial or complete or partial blocking of process lines as well as potential corrosion and must therefore be avoided. Therefore, it is also relevant to be aware of this aspect when defining the process conditions.
- salts e.g. ammonium chloride
- a mixed product stream rich in inorganic halides will be present.
- the stream may be a one-phase gas stream or a two-phase stream with a gas stream rich in hydrogen and hydrogenated hetero-atoms, such as hydrogenchloride and ammonia and a liquid stream comprising mainly hydrocarbons.
- separating the two-phase stream and minimizing the amount of hydrogen halides in the liquid stream comprising hydrocarbons will put fewer demands to corrosion resistance in the choice of materials in process equipment handling this stream.
- a three-phase stream comprising a gas phase, an organic non-polar phase and an aqueous polar-phase, which may be separated in a so-called three-phase separator, possibly in combination with a cascade of separators with intermediate cooling and pressure release.
- the mixed product stream from hydrotreatment would also comprise an amount of ammonia.
- Ammonia and halides may react to form ammonium halide, such as ammonium chloride, which is easily formed and which rapidly solidifies under the appropriate conditions, which are mainly dictated by a precipitation temperature, approximately corresponding to the sublimation temperature of ammonium halide.
- the precipitation temperature is dependent on concentrations and pressure in accordance with thermodynamic principles.
- a water washing process step is also seen, e.g. in the context of nitrogen rich hydrocarbons, which are converted to ammonia, which is highly soluble in water, and which enables withdrawal of hydrogen sulfide as ammonium bisulfide in the wash water.
- concentration of nitrogen hetero-atoms may be above 1 wt %, and the mass ratio of water consumed to hydrocarbon to is typically 1:20 or 1:10, resulting in a concentration of ammonia salts in water around 1 wt % to 5 wt %.
- This design is limited by the concentration of ammonium bisulfide; however, this concentration is allowed to be up to 2 wt % to 4 wt % before corrosion becomes an issue.
- halides are among the hetero-atoms of a hydrocarbonaceous feed, and where they are present in levels above 100 ppm w , it is however necessary to increase the amount of water in the washing process, to achieve quantitative withdrawal of halides from the non-polar phase, while avoiding corrosion issues from elevated halide concentration in the water phase.
- the mass ratio of water to hydrocarbon may be about 1:1, as typical design limits requires keeping Cl levels in the water below 500 ppm w , which corresponds to the requirement for carbon steel or higher alloy steel depending on temperature and pH. This amount of water is 10 to 20 times higher than the normal practice in the refinery industry. If NH 3 or another base is present in the stream, the pH will be higher, and the sensitivity towards presence of Cl will be reduced.
- Such a high amount is of course an economical and environmental challenge, and therefore it is desirable to reduce the amount of water consumed.
- This may be done by providing a means of concentration of the used wash water, such that it is separated in purified wash water and a concentrated brine rich in impurities, such as halides.
- Multiple methods exist for this purpose including membrane filtration, reverse osmosis or evaporation, including falling film evaporation.
- the equipment used in the evaporation process will be much more expensive if special grades of steel are required, so it is also beneficial to consider reducing the corrosiveness of the used wash water, e.g. by neutralizing the used wash water.
- As the wash water in presence of halides typically is acidic, e.g.
- the hydrocarbon stream must be purified to high extent. This may be done by separating the mixed product stream in a high boiling hydrocarbon product, which does not contain relevant amounts of the inorganic gases ammonia or halides and a gaseous product stream comprising essentially all of the inorganic gases. Such a separation may be carried out in equipment of simple design, e.g. a flash drum, which typically will be sufficient if the concentration of chlorides is below 10 ppm.
- This gas stream may contain around 1 ppm w t HCl, which corresponds to a NH 4 Cl precipitation temperature around 180° C. which typically will not pose a problem, as the temperature may be controlled to avoid cold spots and due to the limited amount of NH 4 Cl for precipitation, and therefore such operation is common in traditional fossil refinery plants.
- the liquid:gas distribution becomes 1:8.2, and thus 89% HCl enters the gas phase, and only 11% remains in the liquid phase, which would be 0.6 ppm w t and 110 ppm w t respectively, which still is prohibitively high for the naphtha stream comprising 1000 ppm wt HCl.
- the purity of the high boiling hydrocarbon product will however be higher if a stripping medium is directed to the high boiling hydrocarbon stream, to drive out any gases.
- the stripper To avoid precipitation of ammonium halides in or downstream the separation equipment it is necessary to operate the stripper at an elevated temperature, above the precipitation temperature of the ammonium halides potentially formed from the ammonia and halides present in the stripper overhead stream, i.e. above 150-230° C. or even higher, contrary to the regular operation of a strippers in refinery plants, where they typically operate below or slightly above the boiling point of water, especially if the objective is to drive out gases, since operation of a stripper at elevated temperature will result in an increased loss of product.
- the required stripper outlet temperature is non-linearly dependent on the concentration of NH 3 and HCl in the released gas phase, and therefore the gaseous output of the stripper must be kept above the precipitation temperature, until the gas is washed by contact with washing water.
- the product of the process may be directed to further treatment, either for the production of hydrocarbon transportation fuel of for petrochemical processes, i.e. in a steamcracker.
- FIG. 1 discloses a system for treating a hydrocarbon stream.
- FIG. 1 discloses a system for treating hydrocarbons. Even though some heat exchange units, pumps and compressors are shown in FIG. 1 , further pumps, heaters, valves and other process equipment may be part of the system of FIG. 1 .
- the system of FIG. 1 comprises a sub-system for removing halides from a hydrocarbon stream before the hydrocarbon stream enters a final stripper and/or fractionation section.
- FIG. 1 shows a hydrocarbon stream 2 containing a halide such as chlorine.
- This stream is optionally preheated, before being combined with a hydrogen rich gas stream 6 to a hydrogen enriched hydrocarbon stream 10 in order to ensure the provision of the required hydrogen for the hydrogenation of di-olefins in first reactor 16 .
- the hydrogen enriched hydrocarbon stream 10 is heated in heat exchanger 12 , and optionally by further heating such as a fired heater to form a heated hydrogen enriched hydrocarbon stream 14 .
- the first reactor 16 is optional but may have operating conditions at a pressure of 30 Barg to 150 Barg and a temperature of about 180° C., suitable for hydrogenation of di-olefins.
- the first reactor 16 contains a material catalytically active in olefin saturation and hydro-dehalogenation. Within the first reactor 16 , the heated hydrogen enriched hydrocarbon stream 14 reacts at the presence of the catalytically active material, rendering a first hydrogenated product stream 18 .
- the first hydrogenated product stream 18 is heated, e.g. in a fired heater 20 , and transferred as a heated first hydrogenated product stream 22 to a second reactor 24 where it reacts at the presence of a second catalytically active material.
- quench gas 26 is provided to the second reactor to control the temperature, since hydrogenation reactions typically are very exothermic.
- the first and second catalytically active material may be identical or different from each other and will typically comprise a combination of sulfided base metals such as molybdenum or tungsten promoted by nickel or cobalt supported on a refractory support such as alumina or silica.
- the reaction over the first catalytically active material is dominated by saturation of di-olefins
- the reaction over the second catalytically active material is dominated by saturation of mono-olefins and hydro-dehalogenation of halide-hydrocarbons, but also hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation may take place in the second reactor 24 , depending on the composition of the feedstock.
- the hot mixed product stream 28 may comprise hydrocarbons, H 2 O, H 2 S, NH 3 and HCl, which may be withdrawn by washing and separation.
- the hot product stream 28 is cooled moderately in heat exchanger 32 to form a cooled product stream 30 having a temperature above the precipitation temperature of the mixed product stream.
- the cooled product 30 is directed to a hot stripper 40 where separation is aided by a stripping medium 42 .
- the cooled product 30 is split in a gas product fraction 44 and a liquid product fraction 46 .
- the gas product fraction 44 is combined with a stream of purified water 50 , providing a mixed stream 52 and cooled in cooler 54 , providing a three-phase stream 56 , which is separated in three-way separator 58 , into a light hydrocarbon stream 60 , a contaminated water stream 62 and a hydrogen rich gas stream 66 .
- the hydrogen rich gas stream 66 is directed to a recycle compressor 68 and directed as quench gas 26 for the second reactor 24 and as stripping medium 42 for the hot stripper 40 , as well as recycle gas 8 to be combined with make-up hydrogen gas 4 , forming hydrogen rich gas 6 .
- the light hydrocarbon stream 60 exiting the three-phase separator 58 enters a second stripper 48 to further separate liquid and gaseous components, with the aid of a stripping medium 72 .
- the light ends output 78 from the second stripper 48 is cooled in cooler 80 and directed as a cooled light ends fraction 82 to a further three-phase separator 84 arranged to separate an off-gas fraction 86 from a polar liquid fraction 88 and a hydrocarbon liquid fraction 92 .
- the hydrocarbon liquid fraction 92 from the further three-phase separator 84 is recycled to the second stripper 48 , the polar liquid fraction 88 can be combined with the contaminated water stream 62 and be directed to a means of concentrating 96 , from which a stream of concentrated brine 98 , rich in e.g. NH 4 Cl, as well as a stream of purified water 50 , comprising a low amount of impurities such as NH 4 Cl, are withdrawn.
- the purified water may, typically together with an added amount of water, be added as pure wash water 50 .
Abstract
A process and a system for conversion of a hydrocarbonaceous feed comprising at least 10 ppmw and less than 10000 ppmw of one or more halides, and at least 20 ppmw and less than 10000 ppmw organically bound nitrogen, to a hydrocarbon product stream by hydrotreatment, in the presence of a material catalytically active in hydrotreatment and an amount of hydrogen, wherein said hydrocarbon product stream comprises an amount of ionic halides and an amount of ammonia, said process including:
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- a) separating in a first separation step at a first separation temperature the mixed product stream to provide an overhead stream and a bottoms stream,
- b) combining the overhead stream with an amount of wash water and
- c) separating in a second separation step the combined overhead stream and wash water in a non-polar stream of hydrocarbon product and a polar stream of wash water comprising ammonium halides.
Description
- This invention relates to a process and a system for conversion of a hydrocarbonaceous feed comprising halides and nitrogen, and specifically a process and a system for removing ammonium halides from a hydrocarbon stream comprising ammonia and one or more halides.
- Refinery and petrochemical processes comprise a plurality of treatments of hydrocarbon rich streams in order to provide products or intermediates in the form of LPG, naphtha, gasoline, diesel, etc. Such treatments comprise hydro-treatment, hydro-cracking, steam-cracking, fractionation and stripping, as well as intermediate heat exchange and removal of impurities.
- Hydrocarbonaceous feedstock may, depending on origin, contain heteroatoms, undesired in the downstream processing. The most abundant heteroatoms are sulfur, nitrogen and, oxygen, which may be present in concentrations from 100 ppmw to 10 wt %, and for oxygen in some biological materials even as high as 45 wt %. These heteroatoms are in refinery hydrotreatment processes converted into hydrogen sulfide, ammonia, water and carbon oxides, which cause few challenges in the process plants. Other heteroatoms are typically metals, which typically are present in small amounts (0-10 ppmw) and precipitate on catalyst guard particles, and thus also cause few challenges in the process plants. However, when treating biomass or waste products such as plastic waste, some heteroatoms may be present in much higher concentrations than in fossil feedstocks. For thermally decomposed waste, e.g. pyrolyzed plastic, the content of e.g. Cl may be 1000 ppmw or higher, and after hydrotreatment the organic Cl will have been converted to HCl which may cause corrosion issues, especially if the acidity of HCl is not neutralized by presence of e.g. NH3. It is therefore important to remove the heteroatoms early in the process, to minimize the effect on down-stream process steps. Similar issues may also be observed for biomass comprising halides, e.g. if originating from salt water.
- WO 2015/050635 relates to a process for hydrotreating and removing halides from a hydrocarbon stream by hydrotreatment. The document is silent on the amount of water required for withdrawal of halides from the process and on the practical aspects of the process, except for an emphasis on the materials used being corrosion resistant.
- In addition to halides notably nitrogen is also present in the hydrocarbons feedstocks. During hydrotreatment organically bound nitrogen is converted to ammonia. Ammonia and halides may react to form salts, e.g. ammonium chloride, which is a solid at temperatures below the precipitation temperature which typically is 150° C. to 300° C. Precipitation of such salts may result in partial or complete blocking of process lines as well as potential corrosion and must therefore be avoided. Therefore, it is important to ensure the process temperature to be above the precipitation temperature.
- From 30% or 80% to 90% or 100% of the organic halides in a hydrocarbonaceous feedstock, may be converted to inorganic halides in a hydrocarbon product stream by one embodiment of the disclosure. The hydrocarbon product is washed with water which dissolves inorganic halides and ammonia and may be separated from the hydrocarbon stream.
- By the washing with water, the inorganic halides from the hydrocarbon stream are removed from the product. These inorganic halides removed from the hydrocarbon stream may be taken away from the system in a dilute aqueous wash water solution, or e.g. by regenerating the wash water by evaporation, membrane separation, reverse osmosis or other means of concentrating the impurities in a brine.
- In an embodiment, a make-up hydrogen stream is added to the hydrogen rich gas phase prior to the recycling into the hydrotreatment reactor. This is in order to ensure the required hydrogen to be present within the hydrotreatment reactor for the conversion of organic halides into inorganic halides, and possibly also further reactions, such as olefin saturation.
- Where concentrations are stated in wt % this shall be understood as weight/weight %, and similarly ppmw as parts per million by mass.
- Throughout this text, the term “a material catalytically active in converting organic halides into inorganic halides” is meant to denote catalyst material arranged for and/or suitable for catalyzing the conversion to a commercially relevant extent.
- “Organic halides” are chemical compounds in which one or more carbon atoms are linked by covalent bonds with one or more halogen atoms (fluorine, chlorine, bromine, iodine or astatine—group 17 in current IUPAC terminology).
- “Inorganic halides” are chemical compounds between a halogen atom and an element or radical that is less electronegative (or more electropositive) than the halogen, to make a fluoride, chloride, bromide, iodide, or astatide compound, with the further limitation that carbon is not part of the compound. A typical example of a material catalytically active would be a classical refinery hydrotreatment catalyst, such as one or more sulfided base metals on a refractive support.
- The term “removing halides” is meant to include situations where either some or all of the halides present in organic form are converted into inorganic halides, and subsequently removed. The term is thus, unless otherwise indicated, not limited to situation where a certain percentage of the halides present are removed.
- The term “react at the presence of the catalytically active material” is meant to cover bringing a stream into contact with the catalytically active material under effective conditions for the implied catalytic reaction to take place. Such conditions typically relate to temperature, pressure and stream composition.
- The term “precipitation temperature” of ammonium halides is meant to cover the temperature (under the given conditions, such as concentration and pressure) at which gaseous ammonia and gaseous inorganic halides (typically hydrogen halides) precipitate, either by reacting to form solid ammonium halide crystals or dissolved in condensed water. For ammonium chloride in concentrations above 500 ppmw and a pressure of 100 Barg this temperature is 280° C. as an example, and typically for the relevant conditions this temperature will be in the range 150-300° C.
- The term “thermal decomposition” shall for convenience be used broadly for any decomposition process, in which a material is partially decomposed at elevated temperature (typically 250° C. to 800° C. or perhaps 1000° C.), in the presence of substoichiometric amount of oxygen (including no oxygen). The product will typically be a combined liquid and gaseous stream, as well as an amount of solid char. The term shall be construed to included processes known as pyrolysis, partial combustion, or hydrothermal liquefaction.
- The unit “Barg”, shall in compliance with the practice of the field be used to denote Bar, gauge, i.e. the pressure relative to atmospheric pressure.
- A broad aspect of the present disclosure relates to a process for conversion of a hydrocarbonaceous feed comprising at least 10 ppmw, 100 ppmw or 500 ppmw and less than 1000 ppmw, 5000 ppmw or 10000 ppmw of one or more halides, and at least 20 ppmw, 100 ppmw or 500 ppmw and less than 1000 ppmw, 5000 ppmw or 10000 ppmw organically bound nitrogen, to a hydrocarbon product stream by hydrotreatment, in the presence of a material catalytically active in hydrotreatment and an amount of hydrogen, wherein said hydrocarbon product stream comprises an amount of ionic halides and an amount of ammonia, said process comprising the steps of
-
- a) separating in a stripping process at a first separation temperature the mixed product stream to provide an overhead stream and a bottoms stream,
- b) combining the overhead stream with an amount of wash water and
- c) separating in a second separation step the combined overhead stream and wash water in a non-polar stream of hydrocarbon product and a polar stream of wash water comprising ammonium halides,
- characterized in that the first separation temperature being above the precipitation temperature of the ammonium halides present in the mixed product stream.
- This has the associated benefit of such a method removing halides, especially chloride from the bottoms stream from the first separation step and subsequently from the nonpolar stream of the second separation step, while maintaining a temperature where ammonia and halides are gaseous until an amount of water is available to collect ammonium halides in solution, and thus avoid precipitation of solid ammonium halides on the inner surfaces of the process equipment, by either keeping it in the gas phase or dissolved in liquid water. Furthermore, by the separation before the addition of wash water, the amount of hydrocarbons associated to the stream to be washed by an amount of water is reduced, and thus amount of water required for this washing is also reduced.
- In a further embodiment said stripping process employs hydrogen, steam, methane or nitrogen as a stripping medium. These stripping media have the associated benefits of being available in specific processes. Hydrogen is also a reagent and may be beneficial since no additional reagents are added to the process and as such it is the preferred stripping medium. Steam may be conveniently compatible with the later water addition and methane and nitrogen may also be beneficial due to availability in specific processes.
- In a further embodiment the temperature of said first separation step is above 280° C., 300° C. or 320° C. This choice of temperature has the benefit of being conveniently above the precipitation temperature of the ammonium halides, such that these are maintained in gas phase until combination with water.
- In a further embodiment the temperature of said first separation step is below the temperature at which 30%, 50% or 80% of the mixed product stream boils. This choice of temperature has the benefit of ensuring that at least 70%, 50% or 20% of the mixed product stream is withdrawn as a liquid from the first separator, to minimize the size of equipment in the overhead stream.
- In a further embodiment said polar stream of wash water comprising ammonium halides is directed to a means of concentrating, to provide a stream of purified water and a stream of brine having a concentration of ammonium halides being more than 2 times, 5 times or 10 times and less than 50 times or 100 times above that of the polar stream of wash water comprising ammonium halides. This has the benefit of reducing the amount of wash water consumed by the process and the amount of waste water generated by the process, which is especially relevant if the weight ratio between wash water and hydrocarbon product stream water is above 1:10, 1:5 or 1:2 such as up to 1:1, 2:1 or 10:1.
- In a further embodiment relates to a process for conversion of a raw feed stream rich in molecules comprising C, H, N and one or more halides, and optionally O, Si, and other elements, said process comprising
-
- i. a step of thermal decomposition of said raw feed stream, to provide a precursor to a hydrocarbonaceous feed or a hydrocarbonaceous feed,
- ii. optionally a step of pre-treatment, purifying the precursor to hydrocarbonaceous feed to provide the hydrocarbonaceous feed
- iii. a hydrotreatment step for converting the hydrocarbonaceous feed in the presence of hydrogen, in accordance with any of the previous claims, to provide a hydrocarbon product stream.
- This has the associated benefit of converting a raw feed stream of low value to a hydrocarbon product stream suitable for further processing.
- In a further embodiment said raw feed stream is as a mixture rich in plastic, lignin, straw, lignocellulosic biomass, halide contaminated waste oils or aquatic biological material. This has the associated benefit of transforming such inexpensive or greenhouse gas emission favorable raw materials into a valuable purified hydrocarbon.
- In a further embodiment said hydrotreatment step is followed by the step of directing the hydrocarbon product and/or the bottoms stream to a steam-cracking process.
- This has the associated benefit of providing a raw material for petrochemical processes, from e.g. waste products, biological material or low-cost resources by the steam cracking process which is well suited for providing e.g. alkenes for downstream processing, such as production of polymers.
- A further aspect relates to a system for hydrotreatment of a hydrocarbonaceous stream comprising
-
- (a) a hydrotreatment reactor containing a material catalytically active in hydrotreatment, said hydrotreatment reactor comprising an inlet for introducing a hydrogen enriched hydrocarbon stream and an outlet for withdrawing a first hydrocarbon product stream,
- (b) a first means of separation having at least an inlet, an overhead outlet and a bottoms outlet,
- (c) a means of mixing having two inlets and an outlet,
- (d) a second means of separation, having an inlet and a liquid polar phase outlet, liquid non-polar phase outlet and gas phase outlet,
- wherein said outlet for withdrawing a first product stream is in fluid communication with the inlet of said first means of separation,
- wherein said overhead outlet is in fluid communication with the inlet of said first inlet of the means of mixing,
- wherein a source of water is in fluid communication with the second inlet of the means of mixing,
- wherein the outlet of the means of mixing is in fluid communication with the inlet of the second means of separation and
- wherein at least one of the bottoms outlet of the first means of separation and the liquid non-polar phase outlet of the second means of separation is in fluid communication with a hydrocarbon product outlet or a hydrocarbon fractionator inlet.
- This system has the associated benefit of being well suited for hydrotreatment with purification of the product hydrocarbon stream and the bottoms stream, minimizing the equipment required to be made of high grade steel.
- In a further embodiment of said system for hydrotreatment of a hydrocarbonaceous stream, said first means of separation is a stripper further having a stripping medium inlet. Such a system has the associated benefit of the stripping medium driving dissolved gases, such as ammonia and inorganic halides out of the liquid phase of the hydrocarbon product stream.
- In a further embodiment said system for hydrotreatment of a hydrocarbonaceous stream further comprises a means of concentrating, having an inlet, a concentrated brine outlet and a purified water outlet,
-
- and the liquid polar phase outlet of the means of separation is in fluid communication with the inlet of the means of concentrating,
- wherein the purified water outlet of the means of concentrating is in fluid communication with a second inlet of the means of mixing optionally in combination with a further source of purified water
- and wherein the liquid non-polar phase outlet of the means of phase separation is configured for providing a hydrocarbon product. This system has the associated benefit of being well suited for hydrotreatment with purification of the product hydrocarbon stream with an even further reduced consumption of water.
- The process and the system disclosed may be found useful where the feed to a hydrotreatment process comprises halides. Examples of such feeds include the products of processes such as hydrotreatment of the product from thermal decomposition of halide rich materials, such as waste plastic, comprising e.g. PVC or other halide containing plastics as well as of biological materials with high halide content, e.g. straw and algae, as well as other products of thermal decomposition or hydrothermal liquefication processes, kerogenic feeds such as coal tar or shale oil. The feed comprising halides may also originate from non-pyrolyzed renewable feedstocks, e.g. waste cooking oil, algae lipids, especially when grown in salt water, or other biological feeds comprising hydrocarbons, nitrogen and chloride.
- Ammonia and halides react to form salts, e.g. ammonium chloride, at temperatures below the precipitation temperature typically 150° C. to 300° C. Precipitation of such salts may result in partial or complete or partial blocking of process lines as well as potential corrosion and must therefore be avoided. Therefore, it is also relevant to be aware of this aspect when defining the process conditions.
- After the hydrotreatment of a halide containing hydrocarbonaceous feedstock, a mixed product stream rich in inorganic halides, will be present. Depending on the boiling range and the process temperature and pressure, the stream may be a one-phase gas stream or a two-phase stream with a gas stream rich in hydrogen and hydrogenated hetero-atoms, such as hydrogenchloride and ammonia and a liquid stream comprising mainly hydrocarbons. In the latter case, separating the two-phase stream and minimizing the amount of hydrogen halides in the liquid stream comprising hydrocarbons will put fewer demands to corrosion resistance in the choice of materials in process equipment handling this stream.
- As the hydrogenated hetero-atoms are water soluble, addition of an amount of wash water and cooling the stream, will result in a three-phase stream, comprising a gas phase, an organic non-polar phase and an aqueous polar-phase, which may be separated in a so-called three-phase separator, possibly in combination with a cascade of separators with intermediate cooling and pressure release.
- If the hydrocarbonaceous feedstock comprises an amount of nitrogen, the mixed product stream from hydrotreatment would also comprise an amount of ammonia. Ammonia and halides may react to form ammonium halide, such as ammonium chloride, which is easily formed and which rapidly solidifies under the appropriate conditions, which are mainly dictated by a precipitation temperature, approximately corresponding to the sublimation temperature of ammonium halide. The precipitation temperature is dependent on concentrations and pressure in accordance with thermodynamic principles.
- In traditional refinery processes such a water washing process step is also seen, e.g. in the context of nitrogen rich hydrocarbons, which are converted to ammonia, which is highly soluble in water, and which enables withdrawal of hydrogen sulfide as ammonium bisulfide in the wash water. The concentration of nitrogen hetero-atoms may be above 1 wt %, and the mass ratio of water consumed to hydrocarbon to is typically 1:20 or 1:10, resulting in a concentration of ammonia salts in water around 1 wt % to 5 wt %. This design is limited by the concentration of ammonium bisulfide; however, this concentration is allowed to be up to 2 wt % to 4 wt % before corrosion becomes an issue.
- In a process where halides are among the hetero-atoms of a hydrocarbonaceous feed, and where they are present in levels above 100 ppmw, it is however necessary to increase the amount of water in the washing process, to achieve quantitative withdrawal of halides from the non-polar phase, while avoiding corrosion issues from elevated halide concentration in the water phase. With a feedstock comprising 500 ppmw Cl and a purified hydrocarbon comprising less than 1 ppmw Cl, the mass ratio of water to hydrocarbon may be about 1:1, as typical design limits requires keeping Cl levels in the water below 500 ppmw, which corresponds to the requirement for carbon steel or higher alloy steel depending on temperature and pH. This amount of water is 10 to 20 times higher than the normal practice in the refinery industry. If NH3 or another base is present in the stream, the pH will be higher, and the sensitivity towards presence of Cl will be reduced.
- Such a high amount is of course an economical and environmental challenge, and therefore it is desirable to reduce the amount of water consumed. This may be done by providing a means of concentration of the used wash water, such that it is separated in purified wash water and a concentrated brine rich in impurities, such as halides. Multiple methods exist for this purpose, including membrane filtration, reverse osmosis or evaporation, including falling film evaporation. The equipment used in the evaporation process will be much more expensive if special grades of steel are required, so it is also beneficial to consider reducing the corrosiveness of the used wash water, e.g. by neutralizing the used wash water. As the wash water in presence of halides typically is acidic, e.g. as low as pH=2 for hydrocarbonaceous feedstocks with a low amount of nitrogen, addition of ammonia or sodium hydroxide, either in the wash water or to a stream downstream the addition of wash water, may be used to bring pH to a value in the range 6.5-9.0, which is puts less requirement to materials.
- To minimize presence of halides, the hydrocarbon stream must be purified to high extent. This may be done by separating the mixed product stream in a high boiling hydrocarbon product, which does not contain relevant amounts of the inorganic gases ammonia or halides and a gaseous product stream comprising essentially all of the inorganic gases. Such a separation may be carried out in equipment of simple design, e.g. a flash drum, which typically will be sufficient if the concentration of chlorides is below 10 ppm.
- Gas/liquid separation in a flash drum, will have an efficiency corresponding to the solubility and Henry's law. This will mean that an equilibrium amount of HCl will remain in the liquid phase. At 260° C., 14 MPa the distribution of HCl between liquid and gas is 1:2.7 and accordingly, 6 ppmwt HCl in the inlet to a flash drum will at 260° C., 14 MPa, a be separated in such that 73% HCl (2.7/(1+2.7)) enters the gas phase, and the remaining 27% will remain as 1.7 ppmwt in the liquid phase. In a subsequent low temperature fractionator, this remaining HCl will be released to a gas stream together with NH3. This gas stream may contain around 1 ppmwt HCl, which corresponds to a NH4Cl precipitation temperature around 180° C. which typically will not pose a problem, as the temperature may be controlled to avoid cold spots and due to the limited amount of NH4Cl for precipitation, and therefore such operation is common in traditional fossil refinery plants.
- However, if instead a stream containing 1000 ppmwt HCl is to be separated in a flash drum at 260° C., 14 MPa, approximately 73% HCl will still enter the gas phase, and the remaining 27% will remain as 270 ppmwt in the liquid phase. In a subsequent low temperature fractionator, this remaining HCl will be released to a gas stream together with NH3. This gas stream may contain around 200 ppmwt HCl, which corresponds to a NH4Cl precipitation temperature around 230° C. which requires maintaining cold spots around the low temperature fractionator at a higher temperature and providing a much higher amount of NH4Cl available for precipitation. Therefore, the risk of precipitation and corrosion is much higher.
- If the pressure is reduced from e.g. 14 MPa to 6 MPa, the liquid:gas distribution becomes 1:8.2, and thus 89% HCl enters the gas phase, and only 11% remains in the liquid phase, which would be 0.6 ppmwt and 110 ppmwt respectively, which still is prohibitively high for the naphtha stream comprising 1000 ppmwt HCl.
- The purity of the high boiling hydrocarbon product will however be higher if a stripping medium is directed to the high boiling hydrocarbon stream, to drive out any gases.
- To avoid precipitation of ammonium halides in or downstream the separation equipment it is necessary to operate the stripper at an elevated temperature, above the precipitation temperature of the ammonium halides potentially formed from the ammonia and halides present in the stripper overhead stream, i.e. above 150-230° C. or even higher, contrary to the regular operation of a strippers in refinery plants, where they typically operate below or slightly above the boiling point of water, especially if the objective is to drive out gases, since operation of a stripper at elevated temperature will result in an increased loss of product. The required stripper outlet temperature is non-linearly dependent on the concentration of NH3 and HCl in the released gas phase, and therefore the gaseous output of the stripper must be kept above the precipitation temperature, until the gas is washed by contact with washing water.
- The product of the process may be directed to further treatment, either for the production of hydrocarbon transportation fuel of for petrochemical processes, i.e. in a steamcracker.
-
FIG. 1 discloses a system for treating a hydrocarbon stream. -
FIG. 1 discloses a system for treating hydrocarbons. Even though some heat exchange units, pumps and compressors are shown inFIG. 1 , further pumps, heaters, valves and other process equipment may be part of the system ofFIG. 1 . - The system of
FIG. 1 comprises a sub-system for removing halides from a hydrocarbon stream before the hydrocarbon stream enters a final stripper and/or fractionation section. -
FIG. 1 shows ahydrocarbon stream 2 containing a halide such as chlorine. This stream is optionally preheated, before being combined with a hydrogen rich gas stream 6 to a hydrogen enriched hydrocarbon stream 10 in order to ensure the provision of the required hydrogen for the hydrogenation of di-olefins in first reactor 16. The hydrogen enriched hydrocarbon stream 10 is heated inheat exchanger 12, and optionally by further heating such as a fired heater to form a heated hydrogen enriched hydrocarbon stream 14. The first reactor 16 is optional but may have operating conditions at a pressure of 30 Barg to 150 Barg and a temperature of about 180° C., suitable for hydrogenation of di-olefins. The first reactor 16 contains a material catalytically active in olefin saturation and hydro-dehalogenation. Within the first reactor 16, the heated hydrogen enriched hydrocarbon stream 14 reacts at the presence of the catalytically active material, rendering a first hydrogenated product stream 18. - The first hydrogenated product stream 18 is heated, e.g. in a fired heater 20, and transferred as a heated first
hydrogenated product stream 22 to asecond reactor 24 where it reacts at the presence of a second catalytically active material. Often quenchgas 26 is provided to the second reactor to control the temperature, since hydrogenation reactions typically are very exothermic. The first and second catalytically active material may be identical or different from each other and will typically comprise a combination of sulfided base metals such as molybdenum or tungsten promoted by nickel or cobalt supported on a refractory support such as alumina or silica. Typically, the reaction over the first catalytically active material is dominated by saturation of di-olefins, whereas the reaction over the second catalytically active material is dominated by saturation of mono-olefins and hydro-dehalogenation of halide-hydrocarbons, but also hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation may take place in thesecond reactor 24, depending on the composition of the feedstock. Therefore, the hotmixed product stream 28 may comprise hydrocarbons, H2O, H2S, NH3 and HCl, which may be withdrawn by washing and separation. Thehot product stream 28 is cooled moderately inheat exchanger 32 to form a cooledproduct stream 30 having a temperature above the precipitation temperature of the mixed product stream. The cooledproduct 30 is directed to ahot stripper 40 where separation is aided by a strippingmedium 42. The cooledproduct 30 is split in agas product fraction 44 and aliquid product fraction 46. Thegas product fraction 44 is combined with a stream of purifiedwater 50, providing amixed stream 52 and cooled in cooler 54, providing a three-phase stream 56, which is separated in three-way separator 58, into alight hydrocarbon stream 60, a contaminatedwater stream 62 and a hydrogenrich gas stream 66. The hydrogenrich gas stream 66 is directed to arecycle compressor 68 and directed as quenchgas 26 for thesecond reactor 24 and as strippingmedium 42 for thehot stripper 40, as well as recycle gas 8 to be combined with make-up hydrogen gas 4, forming hydrogen rich gas 6. - The
light hydrocarbon stream 60 exiting the three-phase separator 58 enters asecond stripper 48 to further separate liquid and gaseous components, with the aid of a strippingmedium 72. The light endsoutput 78 from thesecond stripper 48 is cooled in cooler 80 and directed as a cooled light endsfraction 82 to a further three-phase separator 84 arranged to separate an off-gas fraction 86 from a polarliquid fraction 88 and ahydrocarbon liquid fraction 92. Thehydrocarbon liquid fraction 92 from the further three-phase separator 84 is recycled to thesecond stripper 48, the polarliquid fraction 88 can be combined with the contaminatedwater stream 62 and be directed to a means of concentrating 96, from which a stream ofconcentrated brine 98, rich in e.g. NH4Cl, as well as a stream of purifiedwater 50, comprising a low amount of impurities such as NH4Cl, are withdrawn. The purified water may, typically together with an added amount of water, be added aspure wash water 50.
Claims (11)
1. A process for conversion of a hydrocarbonaceous feed comprising at least 10 ppmw and less than 10000 ppmw of one or more halides, and at least 20 ppmw and less than 10000 ppmw organically bound nitrogen, to a hydrocarbon product stream by hydrotreatment, under effective hydrotreatment conditions, in the presence of a material catalytically active in hydrotreatment and an amount of hydrogen, wherein said conversion provides a mixed product stream comprises an amount of ionic halides and an amount of ammonia,
said process comprising the steps of
a) separating in a stripping process at a first separation temperature the mixed product stream to provide an overhead stream and a bottoms stream,
b) combining the overhead stream with an amount of wash water and
c) separating in a second separation step the combined overhead stream and wash water in a non-polar stream of hydrocarbon product and a polar stream of wash water comprising ammonium halides,
wherein the first separation temperature being above the precipitation temperature of the ammonium halides present in the mixed product stream.
2. A process according to claim 1 wherein said stripping process employs hydrogen, steam, methane or nitrogen as a stripping medium.
3. A process according to claim 1 wherein the temperature of said first separation step is above 280° C.
4. A process according to claim 1 wherein the temperature of said first separation step is below the temperature at which 30% of the mixed product stream boils.
5. A process according to claim 1 , wherein said polar stream of wash water comprising ammonium halides is directed to a means of concentrating, to provide a stream of purified water and a stream of brine having a concentration of ammonium halides being more than 2 times and less than 100 times above that of the polar stream of wash water comprising ammonium halides.
6. A process for conversion of a raw feed stream rich in molecules comprising C, H, N and one or more halides, and optionally O, Si, and other elements, said process comprising:
i. a step of thermal decomposition of said raw feed stream, to provide a precursor to a hydrocarbonaceous feed or a hydrocarbonaceous feed,
ii. optionally a step of pre-treatment, purifying the precursor to hydrocarbona-ceous feed to provide the hydrocarbonaceous feed, and
iii. a hydrotreatment step for converting the hydrocarbonaceous feed in the presence of hydrogen, in accordance with claim 1 , to provide a hydrocarbon product stream.
7. A process according to claim 1 , wherein the raw feed stream or the hydrocarbonaceous stream originates from a mixture rich in plastic, lignin, straw, lignocellulosic biomass, halide contaminated waste oils or aquatic biological material.
8. A process according to claim 1 , followed by the step of directing the hydrocarbon product and/or the bottoms stream to a steam-cracking process.
9. A system for hydrotreatment of a hydrocarbonaceous stream comprising
a) a hydrotreatment reactor containing a material catalytically active in hydrotreatment, said hydrotreatment reactor comprising an inlet for introducing a hydrogen enriched hydrocarbon stream and an outlet for withdrawing a first hydrocarbon product stream,
b) a first means of separation having at least an inlet, an overhead outlet and a bottoms outlet,
c) a means of mixing having two inlets and an outlet,
d) a second means of separation, having an inlet and a liquid polar phase outlet, liquid non-polar phase outlet and gas phase outlet,
wherein said outlet for withdrawing a first product stream is in fluid communication with the inlet of said first means of separation,
wherein said overhead outlet is in fluid communication with the inlet of said first inlet of the means of mixing,
wherein a source of water is in fluid communication with the second inlet of the means of mixing,
wherein the outlet of the means of mixing is in fluid communication with the inlet of the second means of separation and
wherein at least one of the bottoms outlet and the liquid non-polar phase out-let is in fluid communication with a hydrocarbon product outlet or a hydro-carbon fractionator inlet.
10. A system for hydrotreatment of a hydrocarbonaceous stream according to claim 9 , where said first means of separation is a stripper further having a stripping medium inlet.
11. A system for hydrotreatment of a hydrocarbonaceous stream according to claim 9 further comprising a means of concentrating, having an inlet, a concentrated brine outlet and a purified water outlet,
and the liquid polar phase outlet of the means of separation is in fluid communication with the inlet of the means of concentrating,
wherein the purified water outlet of the means of concentrating is in fluid communication with a second inlet of the means of mixing optionally in combination with a further source of purified water
and wherein the liquid non-polar phase outlet of the second means of separation is configured for providing a hydrocarbon product.
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WO2016150600A1 (en) * | 2015-03-25 | 2016-09-29 | Haldor Topsøe A/S | Removal of halides from hydrocarbon liquid |
US20190062646A1 (en) * | 2015-11-13 | 2019-02-28 | Sabic Global Technologies B.V. | A catalytic process for reducing chloride content of a hydrocarbon feed stream |
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